Embodiment
The present invention is below described in more detail.
The present inventor pays close attention to the compound that straight chain molecule wherein runs through the inside of the ring of the ring molecule being represented by cyclodextrin, that is, poly-rotaxane, and conscientiously this compound is applied to electrofax charging member by research.As a result, inventor finds can effectively realize above-mentioned purpose by the superficial layer that the poly-rotaxane with ad hoc structure is introduced into charging member, completes thus the present invention.
Superficial layer according to the present invention comprises wherein by the bond of the first poly-rotaxane and the second poly-rotaxane combination.The first poly-rotaxane has the inside that the first straight chain molecule wherein runs through the ring of the first ring molecule, prevents the structure of first ring molecule disengaging the first straight chain molecule thereby the first straight chain molecule has two ends that two end-capping groups and end-capping group be arranged on the first straight chain molecule.The second poly-rotaxane has the inside that the second straight chain molecule wherein runs through the ring of the second ring molecule, prevents the structure of second ring molecule disengaging the second straight chain molecule thereby the second straight chain molecule has two ends that two end-capping groups and end-capping group be arranged on the second straight chain molecule.The first poly-rotaxane and the second poly-rotaxane by forming chemical bond and combination between the first ring molecule and the second ring molecule.
Fig. 1 is the schematic diagram according to poly-rotaxane of the present invention.
Straight chain molecule 2 runs through the inside of the ring of ring molecule 1, and therefore ring molecule 1 is removable in straight chain molecule 2.Therefore, compare with the rubber, the elastic body etc. that wherein have many crosslinking points and bonding point, poly-rotaxane has flexibility.
In addition, thereby the end of straight chain molecule 2 exists end-capping group 3 to prevent that ring molecule from departing from straight chain molecule, and ring molecule is combined.Therefore, in maintaining flexibility, there is loose key (loose bond), and suppress the generation of the C permanent strain causing due to external force.
Become and be apparent that band occurs in the time that charging member becomes unstable with respect to the rotation tracing ability of Electrifier frame, photoreceptor.By inference, there is the poly-rotaxane of combination of flexibility as the material of superficial layer by use, make the formation of roll gap stable thereby the rotational stabilization of charging member increases, therefore can suppress the even generation of density unevenness of the striated causing due to the instability of the formation of roll gap.In addition,, by ring molecule is combined and can reduce the generation of C permanent strain, therefore also can suppress the even generation of density unevenness due to the striated causing of C permanent strain.
< ring molecule >
Any ring molecule all can be used as ring molecule, as long as it can wrap and connect following straight chain molecule.Herein, bag connect finger wherein straight chain molecule run through the state of the inside of the ring of ring molecule.
In the present invention, term " ring molecule " refers to the various annular materials that comprise ring molecule.Term " ring molecule " refers to for molecule or the material of ring-type in fact.Term " ring-type in fact " is intended to comprise not those of closed loop completely, and comprises those with one end of molecule wherein and the superimposed together and helical structure that do not combine of the other end.
Ring molecule is not particularly limited and example can comprise various cyclodextrins (for example, alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, dimethyl cyclodextrin, glycosyl cyclodextrin and derivant or modifier), crown ether-like, benzo-crown ether class, dibenzo dilating ether class, dicyclohexyl crown ether-like (dicyclohexanocrowns) and derivant or modifier.
In cyclodextrin, crown ether-like etc., the size of the ring of ring molecule depends on the kind of ring molecule and changes.Therefore, the ring molecule of use can basis, for example, and hydrophilic/hydrophobic or ionic selection of the thickness of the straight chain molecule of use and straight chain molecule.Especially, be preferably selected from least one cyclodextrin molecular of the group being formed by alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin.
These materials are that become more readily available, cheap and are also the materials that occurring in nature exists, and to connect ability and the physical strength of straight chain molecule good for bag, and are applicable to showing the material of effect of the present invention.
Preferably ring molecule has reactive group in the outside of its ring.This is because in the time that ring molecule combines, can easily carry out by using reactive group to react.Depend on the example of the reactive group of the crosslinking chemical of use, comprise hydroxyl, amino, carboxyl, thiol base and aldehyde radical.In addition, expect to use the group not reacting with end-capping group between the end-blocking formation reaction period as described below.
The straight chain molecule > of <
The straight chain molecule that forms a part for poly-rotaxane is not particularly limited, as long as it is for being connect by ring molecule bag and can integrated straight chain molecule or material in the situation that not using covalent bond.It should be noted in the discussion above that in the present invention, term " straight chain molecule " refers to the molecule of all other materials that comprise macromolecule and meet above-mentioned requirements.
In addition,, in the present invention, the term " straight chain " in " straight chain molecule " refers in fact " straight chain ".That is, if for the ring molecule of rotor rotatable, or when bag connects straight chain molecule ring molecule slidably or mobile, straight chain molecule just can have side chain.In addition,, as long as ring molecule slidably or mobile when bag connects straight chain molecule, straight chain molecule is just flexible or have a spiral fashion.In addition, the length of " straight chain " is not particularly limited, as long as ring molecule slidably or mobile when bag connects straight chain molecule.
The example of straight chain molecule comprises: hydrophilic polymer as polyglycol, polypropylene glycol, PolyTHF, polyvinyl alcohol (PVA) and polyvinyl pyrrolidone, poly-(methyl) acrylic acid, cellulose-based resin (for example, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose), polyacrylamide, polyethylene oxide, Pioloform, polyvinyl acetal be resin, polyvinyl methyl ether, polyamines, polyethyleneimine, casein, gelatin and starch and/or their multipolymer; Hydrophobic polymer as polyolefin-based resins (for example, tygon, polypropylene and with the copolymer resin of other ethylene series monomer), vibrin, Corvic, polystyrene resin (for example, polystyrene and acrylonitritrile-styrene resin resin), acrylic resin (for example, polymethylmethacrylate, (methyl) acrylate copolymer and vinyl cyanide-methyl acrylate copolymer resin), polycarbonate resin, urethane resin, vinyl chloride vinyl acetate copolymer resin and polyvinyl butyral resin; And their derivant or modifier.The example further comprises polyisoprene, polyisobutylene, polybutadiene and dimethyl silicone polymer.Wherein, be preferably selected from the group that formed by polyglycol, polypropylene glycol, polyisoprene and polybutadiene one of at least.
These materials be ability that become more readily available, cheap, that connect by ring molecule bag good, there is high mechanical properties and be applicable to showing the material of effect of the present invention.
The weight-average molecular weight of straight chain molecule is more than 1,000 and 1,000, below 000, preferably more than 3,000 and below 500,000, more preferably more than 5,000 and below 300,000.
Preferably thereby two ends of straight chain molecule have reactive group and easily react with end-capping group described later.Depend on the example of the reactive group of the end-capping group of use, comprise hydroxyl, amino, carboxyl and thiol base.
< end-capping group >
Poly-rotaxane comprises two kinds of molecules, that is, as the ring molecule of rotor with as the straight chain molecule of axle, thereby and end-capping group two ends that are arranged on axle prevent that rotor from departing from axle.Herein, end-capping group refers to comprise the various groups of low-molecular-weight group and high molecular group.
Comprise that use macoradical physically prevents that as end-capping group ring molecule from departing from the method for straight chain molecule thereby provide.In addition, thus give comprise use ionic group prevent that by the ionic repulsion of the ionic and ring molecule of end-capping group ring molecule from departing from the method for straight chain molecule as end-capping group.
The instantiation of end-capping group comprises: dinitro benzene base class is as 2,4-dinitrophenyl and 3,5-dinitrophenyl; Cyclodextrin; Diamantane base class; Trityl class; Fluorescein class; Pyrene class; And derivant or modifier.
< chemical bond >
For poly-rotaxane of the present invention, the ring molecule of the ring molecule of the first poly-rotaxane and the second poly-rotaxane is combined by chemical bonded refractory.Now, the plural poly-rotaxane molecule being combined by chemical bonded refractory can be same to each other or different to each other.In this case, chemical bond can be simple key or the key via various atoms or molecule.
< bonding agent (binder) >
Known bonding agent can be used as the material via chemical bonds ring molecule.The example (for example can comprise cyanuric chloride, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, chloropropylene oxide, dibromobenzene, glutaraldehyde, phenylene diisocyanate, toluene diisocyanate, Toluene-2,4-diisocyanate, 4-diisocyanate), 1,1 '-carbonyl dimidazoles and divinylsulfone.Its further example can comprise that various coupling agents for example, for example, as silane coupling agent (, various alkoxy silanes) and titanium coupling agent (, various alkoxytitaniums).
Its further example can comprise that Stilbene salt system (stilbazolium salt-based) photocrosslinking agent is as formyl stibazole, as by the photocrosslinking agent of photodimerization, and its instantiation can comprise cinnamic acid, anthracene and thymine class with other photocrosslinking agent.
The molecular weight of bonding agent, for being less than 2,000, is preferably less than 1,000, is more preferably less than 600, is most preferably less than 400.
As crosslinked ring molecule, except by by crosslinked above-mentioned ring molecule those that form, also can use the molecule with plural ring shaped molecule structure.In this case, for example, will there is molecule and the straight chain shape molecular mixing of plural ring, and can make the ring that straight chain molecule runs through the molecule with plural ring gather rotaxane to obtain combination.In this case, preferably make straight chain molecule run through ring molecule, after this, the two ends end-capping group end-blocking of straight chain molecule.
The preparation method > of the poly-rotaxane of <
First, by ring molecule and straight chain shape molecular mixing with preparation wherein straight chain molecule run through the poly-rotaxane (pseudopolyrotaxane) of standard of the inside of the ring of ring molecule.
The amount of the ring molecule that straight chain molecule runs through can be controlled by mixing ratio, incorporation time etc. between ring molecule and straight chain molecule.It should be noted in the discussion above that and expect that straight chain molecule does not wrap and is connected in ring molecule thick and fast.When straight chain molecule thick and fast bag while not being connected in ring molecule, keep the degree of freedom of ring molecule with respect to the motility of straight chain molecule, and can obtain and there is the two superficial layer of good flexibility and recovery.
Then, thus two ends of straight chain molecule prevent that with end-capping group end-blocking the poly-rotaxane of standard that ring molecule departs from above-mentioned acquisition from gathering rotaxane to prepare end-blocking.
The combination of the poly-rotaxane of more than two end-blocking is by carrying out the ring molecule of the poly-rotaxane of the end-blocking of acquisition to obtain in conjunction with poly-rotaxane via chemical bonds.
In addition,, except said method, poly-rotaxane can be by using the following ring molecule that wherein more than two ring molecule is combined via chemical bonded refractory to obtain.
The ring molecule that wherein plural ring molecule is combined via chemical bonded refractory and straight chain shape molecular mixing are run through to the poly-rotaxane of standard of ring molecule to obtain straight chain molecule wherein.Then, thus two ends of straight chain molecule prevent that with end-capping group end-blocking ring molecule from departing from straight chain molecule.
< uses the situation > of cyclodextrin as ring molecule
Cyclodextrin is ring molecule, and the inside of its ring is hydrophobic, and utilizes the character that hydrophobic molecule is taken into the inside of ring in aqueous medium.Therefore, usually, use the synthesizing in aqueous medium of rotaxane of cyclodextrin to be undertaken by use hydrophobicity molecular shaft.
< uses the situation > of crown ether as ring molecule
Crown ether is also ring molecule and has the character that cationic molecule is taken into the inside of ring.Therefore, crown ether tends to form rotaxane together with cationic axle shape molecule.This is to use ionic interactional method, therefore, usually, mostly in low polar solvent, reacts.Particularly, preferably crown ether is used as to straight chain molecule as ring molecule and by the molecule with secondary ammonium salt.
Other polymkeric substance of < >
The superficial layer of charging member of the present invention can also comprise other polymkeric substance except above-mentioned poly-rotaxane in the scope of not damaging effect.Now, poly-rotaxane and other polymkeric substance can be combined or can only mix with so-called polymer blending state via chemical bonded refractory.
As other polymkeric substance, for example, can adopt known cementing agent.The example can comprise resin, natural rubber, sulfurized natural rubber and synthetic rubber.
As the resin such as thermoset resin and thermoplastic resin can be used as this resinoid separately.Wherein, fluororesin, polyamide, acrylic resin, urethane resin, silicone resin and butyral resin are preferred.
Ethylene-propylene-diene copolymer (EPDM), Styrene-Butadiene rubber (SBR), silicon rubber, urethane rubber, isoprene rubber (IR), butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), acrylic rubber and epichlorohydrin rubber can be used as synthetic rubber separately.
One in these materials can be used alone, or can be used as potpourri and use them two or more.Also can allow their multipolymer.It should be noted in the discussion above that in these materials, never pollute Electrifier frame, photoreceptor and any other member, and obtain the viewpoint of high release property, any other resin glue of preferably resin being used as superficial layer.
< conductive material >
Preferably further conductive material is added in poly-rotaxane.As conductive particle, provide electron conduction particle and ionic conductivity particle.
Adjuvant > beyond < conductive material
Except above-mentioned conductive material, the filler of being made up of mineral compound etc. can be added into the superficial layer of charging member of the present invention.
The specific insulation > of < superficial layer
The specific insulation of preferred surface layer under the environment of the humidity of the temperature of 23 DEG C and 50%RH is 1 × 103Ω cm is above and 1 × 1015below Ω cm.By the specific insulation of superficial layer is set in above-mentioned scope, keeps the appropriate magnitude of current, and can obtain gratifying image.
< charging member >
Charging member of the present invention has the structure that at least comprises electric conductivity supporting mass and be arranged on the superficial layer on electric conductivity supporting mass.Fig. 2 wherein arranges elastic layer 5 for illustrating on electric conductivity supporting mass 4, and the example of the roll shape charging member (charging roller) of superficial layer 6 is further set thereon, and this figure is vertical with the length direction of roller.
< electric conductivity supporting mass >
For the electric conductivity supporting mass of charging member of the present invention there is electric conductivity and have supporting be arranged on supporting mass as the function of the layers such as superficial layer.As the material for supporting mass, can provide metal as iron, copper, stainless steel, al and ni, and alloy.
< elastic layer >
The rubber providing in the example of the above-mentioned resin glue component as superficial layer and resin can be used as elastic layer material separately.
Its preferred embodiment comprises that epichlorohydrin rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, urethane rubber, silicon rubber and thermoplastic elastomer are as styrene/butadiene/styrene block copolymers (SBS) and styrene/ethylene butylene/styrene block copolymer (SEBS).Wherein, more preferably use polar rubber, because easily carry out resistance adjustment.Also more preferably use epichlorohydrin rubber and NBR, because more easily carry out resistance control and the hardness control of elastic layer.
Even, in the time that the addition of conductive particle lacks, epichlorohydrin rubber also can be brought into play good electric conductivity, because polymkeric substance originally has electric conductivity in middle resistance region.In addition, rubber can reduce the variation with the resistance of position, is therefore suitable as macromolecular elastomer.The example of epichlorohydrin rubber comprises chloropropylene oxide homopolymer, chloropropylene oxide-ethylene oxide copolymer, chloropropylene oxide-allyl glycidyl ether multipolymer and chloropropylene oxide-oxirane-allyl glycidyl ether trimer.Wherein, be particularly suitable for using chloropropylene oxide-oxirane-allyl glycidyl ether trimer, because this trimer shows stable electric conductivity at middle resistance region.The trimeric electric conductivity of chloropropylene oxide-oxirane-allyl glycidyl ether and processability can recently be controlled by random adjusting its degree of polymerization or composition.
The elastic layer that can be formed by epichlorohydrin rubber separately, in using epichlorohydrin rubber as major constituent, can comprise any other general rubber as required.The example of other general rubber comprises ethylene/propylene rubber (EPM), ethylene-propylene-diene copolymer (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubbers, urethane rubber and silicon rubber.Elastic layer can also comprise thermoplastic elastomer as styrene/butadiene/styrene block copolymers (SBS) or styrene/ethylene butylene/styrene block copolymer (SEBS).In the time introducing general rubber, more than its content is preferably 1 mass parts with respect to 100 mass parts elastic layers with material and below 50 mass parts.
Elastic layer preferably has 102Ω cm is above and 1010the specific insulation of measuring under the environment of the humidity at the temperature of 23 DEG C and 50%RH below Ω cm.In addition, in order to adjust specific insulation, can suitably add as conductive particles such as carbon black, conductive metal oxide, alkali metal salts or ammonium salts.In the time that polar rubber is used to material as elastic layer, particularly preferably use ammonium salt.
Elastic layer can be by making to have the plate shape of predetermined thickness or the layer of tube shape and be bonded to electric conductivity supporting mass and form preformed, or by forming with this layer of covering supporting mass.The extruder that selectively, can be provided with crosshead by use is extruded electric conductivity supporting mass and elastic layer material integratedly and is produced elastic layer.
Can adopt if the known methods such as use ribbon mixer, nauta mixer, Henschel mixer, high-speed mixer, Banbury mixer or the mixing of pressure kneader are as the process for dispersing of the materials such as conductive particle, insulativity particle and filler as in elastic layer use material.
From making the uniform viewpoint of roll-gap width with respect to Electrifier frame, photoreceptor along the length direction of charging member, preferred charging member of the present invention has wherein the so-called convex that central portion is thick and thickness reduces to both ends along its length along its length.About projection amount, the preferably external diameter of central portion and be 30 μ m-200 μ m apart from the difference between the external diameter of the position of central portion 90mm.
The formation method > of < superficial layer
Can be dissolved in solvent and by being applied over as impregnating rubbing method on electric conductivity supporting mass superficial layer to be set on electric conductivity supporting mass in connection with the poly-rotaxane of state.Selectively, can carry out following methods: by the solution that wherein makes the poly-rotaxane of end-blocking mix with bonding agent by being applied on electric conductivity supporting mass as impregnating rubbing method; And drying solution is with the method in conjunction with poly-rotaxane.
< verification method >
Poly-rotaxane can pass through the discriminatings such as 1H-NMR, GPC.
< electronic photographing device >
Fig. 3 illustrates the schematic configuration that comprises the electronic photographing device of charging roller according to the present invention.
Electrophotographic photosensitive element 7 has the drum shape that is included in the photographic layer on conductive base.Then, electrophotographic photosensitive element 7 rotarilys actuate with predetermined circle speed (processing speed) along direction indicated by the arrow.
Charging device comprises the charging roller 8 making under predetermined pressure with electrophotographic photosensitive element 7 butts.Charging roller 8 driven rotation along with the rotation of electrophotographic photosensitive element 7, in addition, makes electrophotographic photosensitive element charged to predetermined potential by supplying with predetermined DC voltage from charging with power supply 17.In addition, form device (not shown) as the sub-image for form electrostatic latent image on electrophotographic photosensitive element 7, for example, use as exposure devices such as laser beam flying instrument.Use while irradiating corresponding to the exposure light 14 of image information when the electrophotographic photosensitive element of uniform charged, form electrostatic latent image.
The developer roll 9 providing in developing apparatus 16 is provided to be made near to or in contact with electrophotographic photosensitive element 7, and the in the situation that of discharged-area development, developer roll is that the toner with the polarity identical with the charged polarity of electrophotographic photosensitive element makes that electrostatic latent image is visual and to develop be toner image with carrying out Electrostatic Treatment.Transfer roll 11 is transferred to transfer materials 10 (transfer materials is carried by the paper supplying system with transfer member) by toner image from electrophotographic photosensitive element.Cleaning device has the template of scraping cleaning element 13 and returnable, and mechanically scrapes off the transfer printing remaining toner remaining in after transfer printing on electrophotographic photosensitive element to reclaim toner.Fixing device 12 is made up of warm-up mill etc., and makes the toner image of the transfer printing on transfer materials 10 and gains are expelled to the outside of equipment.
< handle box >
Also can use by will be for example, electronic photographic sensitive structure, charging device, developing apparatus and cleaning device are integrated and obtain, and are designed to removably be mounted to the handle box (Fig. 4) of electronic photographing device.That is, handle box is to comprise integrated charging member each other and as by the handle box of the electrophotographic photosensitive element of charging target, this handle box is removably mounted to the main body of electronic photographing device, and wherein charging member is above-mentioned charging member.In addition, electronic photographing device at least comprises handle box, exposure device and fixing device, and wherein handle box is above-mentioned handle box.
embodiment
Below, be described in more detail the present invention by the mode of specific embodiment.But, the invention is not restricted to following examples.
< produces routine A-1>
(activation of straight chain molecule two ends)
100g polyglycol (is called to PEG below; Weight-average molecular weight: 10,000) be dissolved in 500ml methylene chloride, and solution is placed in argon gas atmosphere.In solution, add 20g1,1-carbonyl dimidazoles, and in argon gas atmosphere, under room temperature, follow stirring to make gained solution reaction 24 hours.
Thus obtained reaction product is injected to the diethyl ether of high-speed stirred.After gains are left standstill to 1 hour, will contain sedimentary centrifugal and separate to take out sediment.Thus, obtain 90g product.
Thus obtained product is dissolved in 500ml methylene chloride, and solution was dropped in 500ml ethylenediamine through 3 hours.After dropping, product is stirred 1 hour.Make thus obtained reaction product be rotated evaporation to remove methylene chloride and to be dissolved in 1 premium on currency.Solution is added to dialysis tube (molecular cut off: 8,000), and dialysis 7 days in water.
With the dry dialyzate obtaining of Rotary Evaporators, and desciccate is further dissolved in 500ml methylene chloride.Solution is added in 1 liter of diethyl ether so that desciccate precipitates again.From contain sedimentary liquid, take out sediment by centrifuging, thereby and sediment vacuum drying at 40 DEG C is obtained to the product (following, referred to as DAT-PEG) that 68g wherein introduces amino two ends of PEG for 2 hours.It should be noted in the discussion above that and also can use the polyglycol-bis--amine being obtained commercially to replace this product.
(preparation of accurate poly-rotaxane)
DAT-PEG that 20g is obtained as mentioned above (weight-average molecular weight: approximately 10,000) and 80g alpha-cyclodextrin at 80 DEG C, be dissolved in pure water, after this, gather rotaxane thereby solution is refrigerated at 5 DEG C to preparation in 24 hours.,, will gather rotaxane vacuum drying 24 hours at 40 DEG C thereafter.
(preparation of the poly-rotaxane of end-blocking)
Will be wherein by 500ml DMF (following, referred to as DMF) and 125ml2, the solution that 4-dinitrofluorobenzene mixes drops in the poly-rotaxane of standard of acquisition described above, and potpourri is reacted under room temperature in argon gas atmosphere.After 24 hours, by 2 liters of dimethyl sulfoxide (DMSO)s (following, referred to as DMSO) thus be added into and in this potpourri, obtain clear solution.Thereby thus obtained solution is dropped to and in the water of 5 liters of vigorous stirring, obtain light-yellow precipitate thing.Sediment is dissolved in 3 liters of DMSO again, thereby and solution is dropped in 0.1% sodium-chloride water solution of 10 liters of vigorous stirring and generate again sediment.Water and methanol wash sediment, and the sediment after washing is carried out to centrifuging.Thereby the vacuum drying at 50 DEG C of thus obtained material is obtained to the poly-rotaxane A-1 of end-blocking of the end-capped that wherein makes straight chain molecule for 24 hours.
< produces routine A-2 to producing routine A-7>
Except using as the straight chain molecule of initiation material changes described in table 1, obtain the poly-rotaxane A-2 to A-7 of end-blocking by the method identical with producing routine A-1.
< produces routine A-8>
(activation of two ends of straight chain molecule)
50,000), 50mg2 by 10g PEG (weight-average molecular weight:, 2,6,6-tetramethyl piperidine oxygen radical (TEMPO) and 0.25g sodium bromide are dissolved in 110ml water.
In thus obtained solution, add the aqueous sodium hypochlorite solution (effective chlorine density: approximately 5%), and follow the at room temperature reaction that stirs the mixture that 2.5ml is obtained commercially.
In the time that reaction is carried out, after interpolation, at once reduce rapidly the pH of system.In order to make pH remain on 10-11,1N NaOH is added in solution to adjust pH.Being reduced in 3 minutes of pH stops, and solution is further stirred 10 minutes.Excessive ethanol is added in solution so that reaction quencher.
With 50ml methylene chloride re-extract three times with extraction the component except inorganic salts, after this, steam methylene chloride with evaporator.
Gains are dissolved in the refrigerator in 250ml hot ethanol and at the temperature of-4 DEG C to hold over night to separate out PEG-carboxylic acid, that is, and the PEG that two ends are replaced by carboxylic acid (COOH), and reclaim the PEG-carboxylic acid of separating out by centrifuging.
Repeat the dissolving circulation of hot ethanol-separate out-centrifuging several times, finally then vacuum drying, thus obtain PEG-carboxylic acid.Productive rate is more than 95%, and carboxylation rate is more than 95%.
(preparation of accurate poly-rotaxane)
The PEG-carboxylic acid that 6g is obtained by said method and 24g beta-schardinger dextrin-are dissolved in the hot water of 70 DEG C that 100ml prepares respectively separately, and two solution are mixed.,, mixed solution is left standstill to 3 days in refrigerator (temperature: 4 DEG C) thereafter.The poly-rotaxane of standard that freeze drying and recovery are separated out with creaminess.
(preparation of the poly-rotaxane of end-blocking)
In the poly-rotaxane of standard of acquisition described above, add the solution wherein 0.26g amantadine, 0.60g bop reagent (benzotriazole-1-base-oxygen base-tri-(dimethylamino) phosphorus hexafluorophosphate) and 0.28ml diisopropylethylamine being dissolved in 120ml dehydration DMF, and fully shake potpourri, hold over night in refrigerator.
, 120ml methyl alcohol be added in gained solution, then stir and centrifuging, then remove supernatant thereafter.Then, the mixed solution of 200ml DMF and methyl alcohol (1:1) is added in gained solution, and carries out twice identical operation.
Further carry out twice identical operation with 200ml methyl alcohol, and by the sediment vacuum drying of acquisition and be dissolved in 140ml DMSO.
Solution is dropped in Isosorbide-5-Nitrae 00ml pure water to separate out poly-rotaxane.The poly-rotaxane of separating out reclaims and vacuum drying by centrifuging.
Thereby further carry out similarly again precipitation operation and obtain the poly-rotaxane A-8 of 16g.
< produces routine A-9 to producing routine A-11>
Except using as the straight chain molecule of initiation material changes described in table 1, obtain the poly-rotaxane A-9 to A-11 of end-blocking by the method identical with producing routine A-8.
< produces routine A-12>
Except using gamma-cyclodextrin to replace the alpha-cyclodextrin as ring molecule, obtain the poly-rotaxane A-12 of end-blocking in the mode identical with producing routine A-1.
< produces routine A-13 to producing routine A-15>
Except using as the straight chain molecule of initiation material changes described in table 1, obtain the poly-rotaxane A-13 to A-15 of end-blocking by the method identical with producing routine A-12.
< produces the synthetic of routine A-16> (synthetic 1) difunctionality crown ether
In argon gas atmosphere, 10.8g (24.1mmol) dibenzo-24-crown ether-8 and 14.0g (99.1mmol) hexamethylene tetramine are dissolved in 50ml trifluoroacetic acid, and thus obtained solution is stirred and spent the night at 80 DEG C.30ml water is added in this solution, and potpourri is at room temperature stirred 2 hours., thereby chloroform be added into in potpourri separation oil reservoir, and under reduced pressure steam the chloroform of oil reservoir thereafter.
By silica gel column chromatography (eluent: first use chloroform, then use 2% methyl alcohol-chloroform mixed solution) thus purifying residue obtains the two formyl bodies (diformyl body) of 10.5g (20.8mmol, 86%) as white solid.
10.5g (20.8mmol) two formyl bodies are dissolved in 120ml THF.,, 3.95g (83.2mmol) lithium aluminium hydride reduction is added in the solution in ice bath to suspend bit by bit, and suspension returning is spent the night thereafter.With the lithium aluminium hydride reduction of saturated aqueous sodium sulfate decomposing excessive, and the solid of separating out is carried out to suction strainer, then with THF washing, and under reduced pressure from filtrate, steam THF.By silica gel column chromatography (eluent: first use chloroform, then use 3% methyl alcohol-chloroform mixed solution) thus purifying residue obtains 8.90g (17.5mmol; 84%) as the glycol of white solid.
Add 2.5ml DMF to dissolve 0.254g (0.500mmol) glycol, and 0.30ml (4.10mmol) thionyl chloride is added in gained solution.Solution is at room temperature stirred to 30 minutes, and add wherein water, then suction strainer, thus obtain 0.214g (0.392mmol; 78%) chloride.First, 0.214g (0.392mmol) chloride and 0.359g then (2.83mmol) thioacetic acid potassium are added in 4.0ml DMF, and potpourri is at room temperature stirred and spent the night.Water is added in solution, then uses chloroform extraction potpourri.Under reduced pressure steam solvent.By silica gel column chromatography (eluent/chloroform) thus purifying residue obtains 0.185g (0.294mmol; 75%) as the difunctionality crown ether that contains thioester substrate of light brown solid.
(synthetic 2)
103g (1.10mol) tert-butyl chloride is added in 51.0g (0.550mol) toluene, and through within 6 hours, adding bit by bit 3.04g (0.0230mol) anhydrous Aluminum chloride.,, potpourri is at room temperature stirred 24 hours thereafter.Potpourri is added in cold dilute sulfuric acid aqueous solution.Then oil reservoir washes with water with saturated aqueous sodium carbonate washing, and with anhydrous magnesium sulfate drying, and under reduced pressure steam solvent (toluene).By distillation purifying residue under reduced pressure, thereby obtain 45.3g (0.222mol) as 3 of water white oil, 5-bis--t-butyltoluene.
The KOH aqueous solution of 40ml5M is added into 21.8g (107mmol) 3, in 5-bis--t-butyltoluene and 86ml (1.07mol) pyridine.,, 37.1g (235mmol) potassium permanganate is added into bit by bit in the gained solution in ice bath and refluxes and spend the night thereafter.300ml2M sulfuric acid is added in solution, then suction strainer, and wash residue with water and then wash with ethyl acetate.Use anhydrous magnesium sulfate drying organic layer, and under reduced pressure steam solvent.Thereby with normal hexane recrystallization residue acquisition 9.83g (41.9mmol; 16%) as 3 of white solid, 5-bis-uncles-benzoic acid.
By 14.41g (18.8mmol) 3,5-bis--tert-butyl benzoic acid is added in 10.0ml (137mmol) thionyl chloride.Potpourri is stirred and spent the night at 50 DEG C, after this, under reduced pressure steam excessive thionyl chloride.In addition, benzene is added in gained solution, then azeotropic distillation, thus remove residual thionyl chloride.Under ice bath, will drop to bit by bit by 4.32g (56.4mmol) 3-amino-1-propyl alcohol is added in the solution obtaining in 20ml THF by synthetic as mentioned above acyl chlorides being dissolved in to the solution obtaining in 20ml THF.After dropping, gained solution is at room temperature stirred 2 hours.Then, add the HCl of 50ml water and 100ml3M, and be extracted with ethyl acetate solution.Use anhydrous magnesium sulfate drying extract, and under reduced pressure steam solvent.Thereby drying under reduced pressure residue obtains 5.17g (17.7mmol; 94%) as the acid amides of white solid.
Add 50ml THF to dissolve 5.17g (17.7mmol) acid amides., 2.50g (52.8mmol) lithium aluminium hydride reduction be added in solution in ice bath, and potpourri is refluxed and spent the night thereafter.After backflow, saturated aqueous sodium sulfate is added into the lithium aluminium hydride reduction with decomposing excessive in potpourri.Gained solution is carried out to suction strainer, and with ethyl acetate washing solid and under reduced pressure steam solvent from filtrate.
By silica gel column chromatography (eluent: first use chloroform, then use 3% methyl alcohol-chloroform mixed solution) purifying residue, thereby obtain the amines of 4.78g (17.3mmol) as water white oil.Add 40ml methyl alcohol to dissolve amines, and follow stirring that 40ml10%HPF6 is added in the solution in ice bath bit by bit.The white solid of separating out is carried out to suction strainer.In addition, 100ml water is added in white solid, then filters, thereby and by the cooling combined filtrates white solid of separating out, then suction strainer.Repeat this operation three times.,, with acetonitrile washing white solid and filtration, and use anhydrous magnesium sulfate drying filtrate thereafter.Under reduced pressure steam the solvent of filtrate, then drying under reduced pressure, thus obtain 7.15g (16.9mmol; 95%) as the compound of the following formula (1) of white solid.This compound is for the production of rotaxane.
[Chemical formula 1]
(synthetic 3)
synthesizing of the PolyTHF of phenylene diisocyanate end-blocking:
4ml chloroform is added in the anhydrous PolyTHF of 0.624g (0.624mmol).In argon gas atmosphere, this solution is dropped at leisure by 1.00g (6.24mmol) m-benzene diisocyanate is added in the solution obtaining in 10ml chloroform., 18.9mg (30.0 μ mol) di-n-butyltin dilaurate be added in solution, then at room temperature stir 1 day thereafter.Thereby obtain the PolyTHF as the phenylene diisocyanate end-blocking of white solid by distillation purifying gained solution.
(synthetic 4)
the production of poly-rotaxane:
Add 1.5ml chloroform and synthesize to dissolve the difunctionality crown ether and the 276mg (0.653mmol) that obtain in 430mg (0.684mmol) synthetic 1 compound obtaining in 2.,, in this solution, add the PolyTHF that the 386mg (0.311mmol) being dissolved in 0.50ml chloroform synthesizes the phenylene diisocyanate end-blocking obtaining in 3 thereafter.Then, 42mg (60 μ mol) di-n-butyltin dilaurate is added in gained solution, then at room temperature stirs 1 day.Thereby the fraction classification of high molecular weight material in preparation GPC is obtained to 838mg (importing rate: 80%) as the poly-rotaxane of light brown solid.
Add 2.00ml DMF to dissolve the poly-rotaxane of 820mg (0.286mmol), and 0.29ml (2.10mmol) triethylamine is added in this solution., 0.180ml (1.80mmol) acetic anhydride be added in this solution, then stir 12 hours thereafter.Then, 30ml2M hydrochloric acid is added in this solution, and with chloroform extraction solution and use anhydrous magnesium sulfate drying.Then, under reduced pressure steam solvent, then by preparation GPC purifying, thereby obtain the poly-rotaxane of following N-acetylation of 681mg as white solid.
Then, under argon gas atmosphere, add the degassed methyl alcohol of 30ml to dissolve 0.509ml (4.50mmol) acetyl chloride.Under argon gas atmosphere, 20ml methanol solution is added in the poly-rotaxane of 404mg N-acetylation, then reflux 8 hours.Under reduced pressure steam solvent, then drying under reduced pressure, thus obtain the end-blocking poly-rotaxane A-16 of 403mg as yellow solid.Poly-rotaxane has four thiol bases.
[table 1]
Table 1
< produces the production of routine B-1> conductive particle
In hand wheel mill (edge runner), 140g methylhydrogenpolysi,oxane is added into 7.0kg silica dioxide granule (mean grain size: 15nm; Specific insulation: 1.8 × 1012Ω cm) in, and under the linear load of 588N/cm (60kg/cm), content is under agitation mixed 30 minutes.Now stirring rate is 22rpm.In hand wheel mill, through adding 7.0kg carbon black " #52 " (trade name is manufactured by Mitsubishi Chemical Corporation) in 10 points of clockwise potpourris.Under the linear load of 588N/cm (60kg/cm), gained potpourri is under agitation further mixed 60 minutes.Therefore, carbon black is adhered to be coated with the surface of the silica dioxide granule of methylhydrogenpolysi,oxane, after this, by using dryer by silica dioxide granule at 80 DEG C dry 60 minutes, to produce composite conductive particle.Stirring rate is now 22rpm.The mean grain size that it should be noted in the discussion above that the composite conductive particle of each acquisition is 15nm, and its specific insulation is 1.1 × 102Ω cm.
< produces the production of routine C-1> resilient roller
With resinoid (" Metaloc U-20 " trade name, is manufactured by Toyokagaku Kenkyuusho Co.Ltd.) thus coating diameter is 6mm and length rod that to be 252.5mm be made up of stainless steel and dry as electric conductivity supporting mass.Be thereby that the hermetic type mixer of 50 DEG C mixes and mediates 10 minutes raw materials complexs by material described in table 2 with being adjusted to temperature.
[table 2]
Table 2
Sulphur using 0.8 mass parts as vulcanizing agent, 1 mass parts are added in raw material complex as dibenzothiazyl disulfide (DM) and the 0.5 mass parts list sulfuration tetra methylthiuram (TS) of vulcanization accelerator, and with being cooled to the end runner mill of temperature of 20 DEG C by potpourri kneading 10 minutes.Therefore, obtain elastic layer compound.
Then, the extrusion moulding machine crude rubber composition (elastic layer complex) that has the crosshead shown in Fig. 5 by use is using the cylindric electric conductivity supporting mass covering coaxially as central shaft, thereby obtains the diameter that wherein external diameter of crude rubber composition layer is 9mmcharging member preparation formed body 19.Crosshead 21 is for being generally used for the device of coated cable or electric wire, and the rubber discharge portion of barrel by being mounted to extruder 20 is used.
Then, in electric oven, at 160 DEG C, charging member preparation formed body 19 vulcanize and curing 1 hour of bonding agent.Cut the both ends of rubber, become after the rubber length of 228mm, surface grinding is processed into the diameter that the external diameter of its central roll central portion is 8.5mmroll shape, thereby on electric conductivity supporting mass, form elastic layer, obtain thus resilient roller.The projection amount (central portion and poor apart from the external diameter between the position of central portion 90mm) of roller is 120 μ m.
embodiment 1
The production > of < charging roller 1
Produce mixed solution based on the formula described in table 3.
[table 3]
Table 3
| End-blocking gathers rotaxane A-1 | 100 mass parts |
| Conductive particle (produce in routine B-1 and produce) | 40 mass parts |
| 1N sodium hydrate aqueous solution | 500 mass parts |
191.55g mixed solution is put into the vial of the internal volume with 450ml with 200g together with the beaded glass of the volume average particle size separately with 0.8mm of medium, and paint stirring dispersion machine and disperse 12 hours.,, from mixed solution, remove beaded glass thereafter.
To wherein the solution being dissolved in as the cyanuric chloride of cementing agent in 1N sodium hydrate aqueous solution be mixed in the poly-rotaxane solution of end-blocking that conductive particle is disperseed wherein to obtain by aforesaid operations.Thus, preparation table surface layer coating fluid.
By using superficial layer coating fluid to carry out single-steeping coating by producing the resilient roller of producing in routine C-1.At room temperature dry resilient roller, and carry out the association reaction that end-blocking gathers rotaxane, wherein in resilient roller, form the charging roller by the superficial layer of making in conjunction with poly-rotaxane thereby obtain.
In this case, carrying out dip coated, to make dip time be 9 seconds, and initial stage dip-coating pulling speed is 20mm/s, and final dip-coating pulling speed is 2mm/s, and speed reduces along with the time between initial stage and final speed is linear.Differentiate by 1H-NMR and GPC in conjunction with poly-rotaxane, and confirm to obtain the poly-rotaxane of expecting.
In addition, be coated with the sheet of being made by fluororesin to form film with superficial layer coating fluid, and carry out in the same manner as described above the association reaction of the dry and poly-rotaxane of end-blocking of film at normal temperatures, thereby on the sheet of being made by fluororesin, form by the thin layer of making in conjunction with poly-rotaxane.
When the thin layer obtaining together with the sheet of being made by fluororesin when observing the small-angle neutron scattering pattern of thin layer obtaining in single shaft direction stretches, observe common butterfly pattern.In addition find along with stretching scattering strength reduces.
In the case of measuring in the same manner as described above the sheet of being made up of common cross-linked rubber etc., fixing crosslinking points distributes in inhomogeneous mode, therefore observes abnormal butterfly pattern.In addition,, along with stretching unevenness increases, therefore scattering strength is generally tended to increase.In addition, think and make to show the reduction of common butterfly pattern and scattering strength due to following reason: according to the poly-rotaxane of the combination of the present embodiment because crosslinking points freely moves, and have loose key as shown in Figure 1, so get the configuration that relaxes uneven texture and strain at coating interior with Ad hoc mode.
The evaluation > of < charging roller 1
(evaluation of the striated image causing due to band)
As the electronic photographing device with the structure shown in Fig. 3, the transformation color laser ink-jet printer (trade name: HP Color LaserJet4700dn) manufactured by Hewlett-Packard Co.Ltd., makes the output speed (A4 longitudinal output) of the recording medium with 200mm/sec.Image resolution ratio is 600dpi, and once charging is output as-1, the DC voltage of 100V.
As the handle box with the structure shown in Fig. 4, use the handle box (black is used) for printer.
From above-mentioned handle box, take out subsidiary charging roller, and charging roller 8 is installed.Making charging roller 8 and Electrifier frame, photoreceptor 23 is at one end butt (Fig. 6) under the spring pressure (two ends add up to 9.8N) of 4.9N.
Handle box left standstill under the environment of the humidity of the temperature of 15 DEG C and 10%RH more than 12 hours and be arranged on equally under the environment of the humidity of the temperature of 15 DEG C and 10%RH in standing more than 12 hours above-mentioned electronic photographing device, and in identical environment output image.As evaluation map picture, output half tone image (with the width of 1, the direction vertical with the sense of rotation of Electrifier frame, photoreceptor, draw the image of horizontal lines with the intervals of 2).Whether visualization output image there is the striped and the degree thereof that cause due to band, and standard evaluation based on described in table 4.
[table 4]
Table 4
| Grade A | Do not recognize striped |
| Grade B | Recognize slight striped |
| Grade C | Recognize striped clearly |
(evaluation of the striated image causing due to C permanent strain)
Charging roller 8 is mounted in the handle box of the handle box that is different from picture appraisal described above, and makes this handle box leave standstill 1 month under the environment of the humidity of the temperature of 40 DEG C and 95%RH.Then, handle box is mounted to electronic photographing device by handle box leave standstill 6 hours under the environment of the humidity of the temperature of 23 DEG C and 50%RH after, and under identical environment output image.As evaluation map picture, output half tone image (with the width of 1, the direction vertical with the sense of rotation of Electrifier frame, photoreceptor, draw the image of horizontal lines with the intervals of 2).Whether visualization output image there is the striated image and degree and the standard evaluation based on described in table 5 that cause due to C permanent strain.
[table 5]
Table 5
| grade A | do not recognize the generation of striped. |
| grade B | recognize slightly the generation of striped. |
| grade C | clearly recognize the generation of striped. |
(measurement of C set deformation volume)
After output image, from handle box, take out charging roller 8, and measure respectively the radius with respect to the abutting part of Electrifier frame, photoreceptor and the charging roller of non-abutting part.For measurement, use by Tokyo Opto-Electronics Co., Ltd. manufacture from action roller measurement mechanism.
About three positions: along the central portion of the length direction of charging roller, and from central portion to the left with the position of right side 90mm, charging roller 1 is at every turn with 1 ° of rotation, and measures the position corresponding to abutting part and non-abutting part.Then, calculate poor between the maximal value of radius of non-abutting part and the minimum value of the radius of abutting part.The value that is three position maximums by semidiameter is defined as C set deformation volume.
embodiment 2-20
The production of < charging roller 2-20 and evaluation >
Except poly-end-blocking rotaxane and cementing agent are changed described in table 6, by the method acquisition charging roller 2-20 identical with embodiment 1.Evaluate charging roller in the mode identical with the evaluation method of the charging roller 1 described in embodiment 1.
[table 6]
Table 6
| Embodiment | Charging roller numbering | The production example of the poly-rotaxane of end-blocking | Cementing agent |
| 1 | 1 | A-1 | Cyanuric chloride |
| 2 | 2 | A-1 | Tetraethoxysilane |
| 3 | 3 | A-1 | 1,1-carbonyl dimidazoles |
| 4 | 4 | A-1 | 2,4-toluene diisocyanate |
| 5 | 5 | A-1 | Tetraethoxysilane |
| 6 | 6 | A-2 | Cyanuric chloride |
| 7 | 7 | A-3 | Cyanuric chloride |
| 8 | 8 | A-4 | Cyanuric chloride |
| 9 | 9 | A-5 | Cyanuric chloride |
| 10 | 10 | A-6 | Cyanuric chloride |
| 11 | 11 | A-7 | Cyanuric chloride |
| 12 | 12 | A-8 | Cyanuric chloride |
| 13 | 13 | A-9 | Cyanuric chloride |
| 14 | 14 | A-10 | Cyanuric chloride |
| 15 | 15 | A-11 | Cyanuric chloride |
| 16 | 16 | A-12 | Cyanuric chloride |
| 17 | 17 | A-13 | Cyanuric chloride |
| 18 | 18 | A-14 | Cyanuric chloride |
| 19 | 19 | A-15 | Cyanuric chloride |
| 20 | 20 | A-16 | TDI |
TDI: toluene diisocyanate
comparative example 1
The production of < charging roller 21 and evaluation >
Except not using cementing agent, obtain charging roller 21 in the mode identical with embodiment 1.Evaluate charging roller in the mode identical with the evaluation method of the charging roller 1 described in embodiment 1.
comparative example 2
The production of < charging roller 22 and evaluation >
To produce the mode that pseudorotaxane is identical in routine A-1 and prepare pseudorotaxane with producing.This pseudorotaxane is defined as to pseudorotaxane 17.Except using pseudorotaxane 17 to replace end-blocking to gather rotaxane A-1, and do not use beyond cementing agent, obtain charging roller 22 in the mode identical with charging roller 1.Evaluate charging roller in the mode identical with the evaluation method of the charging roller 1 described in embodiment 1.
comparative example 3
The production of < charging roller 23 and evaluation >
Except using the potpourri described in table 7 to replace the poly-rotaxane A-1 of end-blocking, obtain charging roller 23 in the mode identical with embodiment 1.Evaluate charging roller in the mode identical with the evaluation method of the charging roller 1 described in embodiment 1.
[table 7]
Table 7
| PEG (weight-average molecular weight: 10,000) | 50 mass parts |
| α – cyclodextrin | 50 mass parts |
| DNF | 2 mass parts |
| Cyanuric chloride | 3 mass parts |
Table 8 illustrates the evaluation result of embodiment 1-20 and comparative example 1-3.
[table 8]
Table 8
The application requires the rights and interests of the Japanese patent application 2011-277619 submitting on Dec 19th, 2011, by reference to its entirety is incorporated herein.
description of reference numerals
1 ring molecule
2 straight chain molecules
3 end-capping groups
4 electric conductivity supporting masses
5 elastic layers
6 superficial layers
7 electrophotographic photosensitive elements
8 charging rollers
9 developer rolls
10 transfer materials
11 transfer rolls
12 fixing devices
13 cleaning elements
14 exposure light
15 flexible adjustment scraper plates
16 developing apparatuss
17 power supplys
18 toner seals
19 charging member preparation formed bodys
20 extruders
21 crossheads
22 electric conductivity supporting mass conveying rollers
23 electrophotographic photosensitive elements